Detergent sulphonic acid and sulphate salts of certain amphoteric detergents



United States Patent F DETERGENT SULPHONIC ACID AND SUL- PHATE SALTS OF CERTAIN AMPHOTERIC DETERGENT S Hans S. Mannheimer, New York, N. Y., assignor to John J. McCabe, Jr., New Brunswick, N. 5., and said Mannheimer, as joint venturers No Drawing. Application December 8, 1955, Serial No. 551,745

7 Claims. (Cl. 260-401) This invention relates to novel compositions and to methods for producing them. In one of its more specific aspects, the invention is directed to the method of making and to novel derivates of metal salts of substituted amido, amino acids, to which I shall hereinafter refer to as amino acid metal salts.

Said amino acid metal salts have been found useful as detergent, foaming, wetting, emulgating, emulsifying and dispersing agents. They are surface active agents, and serve as excellent synthetic detergents, dye assistants and softeners in the textile and related fields.

Said amino acid metal salts, employed as starting materials in the practice of this invention, have the following general Formula I:

'11 R2-OH RC0-NR2-N Rz-CO OM in which R is an organic radical, which, if connected to a carboxyl group, provides a monocarboxylic acid, and said radical contains at least 4 carbon atoms and for most purposes is a hydrocarbon radical of 418 carbon atoms; R1 is hydrogen or an aliphatic hydrocarbon radical having 1-4 carbon atoms, such as CI-Is, -C2H5, C3H7, and C4H9 or any one of said radicals having one or more of the hydrogens thereof which has been hydroxy substituted, illustrative examples of which are C2H4OH, CH2CHOHCH3, --CHOHCHOHCH2OH or any one of said radicals, but of 2-4 carbon atoms and whose hydrogens have been either unsubstituted or hydroxy substituted and having a single ether (O-) or keto (CO-) linkage therein, illustrative examples of which are C2HaOCH3, -C2H4OC2H4OH,

R2 is a hydrocarbon group having 1-4 carbon atoms, such as -CH2-, --C2H4, -C3Hs and C4Hs-, or any one of the aforesaid groups, any one or more of whose hydrogens has been hydroxy substituted, illustrative ex amples of which are butyl amino hydroxy propyl acetol amine 2,781,376 Patented Feb. 12, 1957 ice One of the methods which may be employed is to first react an hydroxy diamine with an organic acid in the molecular proportion of l to 1. When approximately 1 mole proportion of water of reaction has been formed and the acid number of the mass is zero, the reaction is terminated, and the resulting reaction mass under specific and controlled conditions is reacted with a metal salt of a monohalomonocarboxylic acid to provide an amino acid metal salt defined in Formula I.

The organic acid reacted with said diamine is one containing a single COOH group or any of the available anhydrides of said acids and by the term monocarboxylic organic acid as used herein, I mean to include both the acid and the anhydride thereof which I regard as the equivalent of the acid. These acids may be: the aliphatic open chain saturated or unsaturated fatty acids as well as said fatty acids containing hydroxy or keto groups and/or other substituents, such as aryl radicals, as for example, acids of the type of Twitchell fatty acids; cycloaliphatic carboxylic acids preferably containing no more than 4 condensed nuclei and examples of which are hexahydrobenzoic, resinic, and naphthenic acids; heterocyclic aliphatic carboxylic acids, such as the various pyridine carboxylic acids.

While carboxylic acids having any number of carbon atoms may be employed, I prefer to employ those having at least 5 carbon atoms and preferably 5-19 carbon atoms in straight chain relationship. The acids which I employ may be derived from a number of different sources. Among some of them are the acid components chosen from oil or fats of animal, marine or vegetable origin and these include; the acids of cocoanut, palm kernel and palm oil, also from soy bean, linseed, olive, rapeseed, cottonseed, peanut and castor oil which contain largeproportions of unsaturated hydroxy fatty acids and also the acids derived from tallow, fish and seal oils, whale or shark oils and the hydrogenated acids from these sources. Moreover, the synthetic high molecular weight fatty acids, obtained by the oxidation of parafiin wax and similar high molecular weight hydrocarbons by means of gaseous oxidizing agents may be employed. In addition the acid may be one of the resinic acids, such as abietic acid, or the naphthenic acids and long chain fatty acids having an aromatic hydrocarbon radical connected diretly with the aliphatic chain (Twitchell fatty acids) as are obtainable from oleic, ricinoleic, linoleic and similar unsaturated fatty acids. Instead of employing mixture of acids from oil, fats and resins, single acids may be used, for example, caproic, pimelic, heptylic, caprylic, undecylic, lauric, pahnitic, stearic, behenic, arachic, cerotic, oleic, erucic, linoleic, linolenic, ricinoleic and hydroxystearic acids.

Of the aforesaid diamines I prefer to employ aminoethylethanolamine hereinafter referred to as reactant A. Because it is commercially available in large quantities, its use provides for efiicient production of some of the starting materials.

Examples of some of the other diamines which may be employed in the production of starting materials are methyl amino isopropyl isopropanol amine (CHsNHCaHsNHCsHeOH) amino isobutyl isobutanol amine (NH2C4HsNHC4HaOI-I) amino hydroxypropyl propane diol amine (NHZC3H5OHNHC3H4(OH)2) propyl amino ethoxy ethyl ethoxy ethanol amine (C3H7NHC2H4OCzH-iNHC2H4OCaH4OH) (C4H9NHC3H5OHNHCHaCOCH2OH) ethyl amino propanone ethanol amine (C2H5NHCH2C0CH2NHC2H4OH) respectively, hereinafter referred to as reactantsiByCyD, E, F and G.

The reactants AG respectively.maylbeproduced'by employing a number of different classical methods well known to the art. reacting ammonia with a compound which is the dichloride of the R2 group between the two nitrogens and has formula Cl'Rz-Cl, and subsequently'treating the diamine produced with caustic soda to' remove HCl which is attached. Thenthe resultant. diamine is reacted with a compound .of'the' formula CllRz-OH, and"if R1 is other than-.liyd'rogen, another reactant Ri- CI is used. Again, the hydrochloride 'is removed. In this manner, the various diamines employed in the producti'on of'my starting .materials' may. bet-produced and are of the following formula:

in which R1 and Rzhave heretofore' b'een defined.

Oneof the well-known commercial methods employed in the productionof said diamine'swhose general formula isabove set forth is-predicated upon thereaction of epoxy compounds, such as, ethylene o'xide,-'-prop'ylene oxide, etc., with ammonia to form theiintermediatediamine which is subsequently reacted with additional epoxy compoundin the presence jof 'water.

Amongso'ineof the salts of the halo acids which may be employed are the sodium and potassium salts of monochloracetic acid, monochlorpro'pionic acidfrnonochlorlactic acid, monochlorhydroxyacetic acid obtainable from 'di-chloi'ac'e'tic acid, monochloracetoace'tic acid, monochlorethoxyacetic acid, etc.

One of the general types of method which may be employed'for the production of some of these starting materials consists in first' reacting one mol of a monocarboxylic acid having at least 4 carbon 'atoms'in its radical connected to its COOH group with one mol of one of said diamines, examples ofwhi'ch are reactants A-F, until only approximately 1 mol of water has been removed. In carrying out this reaction the mixture is first h'eatedto about 110-180" C. in vacuum'of 90-130 mm. of mercury pressure until one mol of water of reaction has been produced and removed. (All of the terms mm. and 'mm. pressure as used in'this entire description are intended to mean mm. of mercuryjpressure.) 'The reaction mass is then allowed toco'ol "to room temperature and is then at elevated temperatures reacted with a monohalocarboxylic acid in' the presence of 2 mols of caustic soda in aqueous solution. "In one of its preferred forms one mol of said'reaction 'mass'ds added to an aqueous solution containingone r n ol -of the monohalocarboxylic and 2 mols of caustic 's'odaj wh'ich solution prior to the addition has been prepared and maintained at a temperature no greater than 20 C. The mix is heated to a temperature of 95 C. until the pH has been reduced fromabout 13 to 8-8.5 and *th'ereis no further change in pH upon continued heating' atsaid temperature.

Another' method which may be employed for produc starting materials of Formula I in the practice of this invention is as follows: 7

The reaction mass of the monocarboxylic acid and the diamine, an example of which is product X, is heated to 90- 10? (3. and there is gradually added thereto an equi-molecular proportion of monohalornonocarboxylic acid, such as monochloracetic acid, whereupon exothermic reaction occurs and the temperature rises from 90-100 C. to about Bil-160 C. The resul'tant is allowed to cool to 100 C. and is then dissolved in water. To this solution is added an aqueous solution containing 2 mols of caustic soda for each mol of monochlbn One method consists essentially in acetic acid previouslyused. This mass is stirred for about 15 minutes at a temperature of about 60 C. The

resultant product is a reaction product as defined in Formula I.

Still another method which may be employed for the production of the intermediate, known herein as product X, is to react an acid chloride, having the general formula R-CO-Cl, R being heretofore defined, with the diamine in the presence of water and caustic soda.

The following are illustrative examples given =merely for the purposes, of specifically illustrating how some of the starting materials employed'in the practice of the present invention may be produced, all parts being given by weight unless otherwise specified:

EXAMPLE A 200 parts of lauric acid and 104 parts of reactant A are placed in a reacting vessel and are heated sufiiciently to melt the lauric acid whereupon an agitator located therein is started and mixes and maintains these com ponents in'mixedco'ndition. While being constantly agitated the mix isheated under vacuum of about 110 mm; pressure for about 3 hours while'gradually raising the'temperature to 170 C. 'During this period 18' parts of water have been formed and distilled 'ofi, leaving behind areaction mass having an acid number of approximately zero. Then this reaction mass, herein known as Product X, is allowed to cool to room temperature and the entire mass is added too. previously prepared solution produced by adding 96 parts of monophlo'race tic acid and 80 parts of caustic soda to 300' parts of'water. This solution was prepared and maintained at a temperature below 20 C. 'before the addition of said reaction mass. This mixture is heated to 95 C. and maintained at this temperature for 2 hours. During this period the pH of the mix is reduced from approximately 13 to 8 8.5. At the end of this period the pH of this mass is no longer subject to change by continued heating at said temperature and a sample of the resulting product is watersoluble to a sparkling clear'solution. At the end of this period the mass consists chiefly ofa water solution of one of my starting materials, hereinafter known as product A and having the following formula:

a period of l hourto 95 C. The mass is subsequently maintained nuns temperature of 95 Cfun'til there is no change in pI-Lthis taking'approximately 2 to 3' hours. Thereaction mass consists'essential-ly ofanlaqueous solution of another one of my starting materials, hereinafter known as product 13, and having the formula which is the' same I as that of Example A, except that 20 C. Ihe resulting mixture is then'heat'ed under -"the same conditions as outlined in Example A until the re- "suitingproduct for-ms sparkling "clear-aqueous solutions and is no longer subject to pH change in continued heating. At the end of this period the mass consists chiefly of an aqueous solution of one of mystarting materials,-

hereinafter known as product C, and having the formula the same as that of Example A, except that CsHis is substituted for C11H23 therein, and C2H4 for the CH2.

EXAMPLE D 282 parts linseed fatty acid and 104 parts reactant A are treated in the same manner as described in Example A. The entire reaction mass is then processed with an aqueous solution of 96 parts monochloracetic acid and 80 parts of caustic soda previously made and maintained below 20 C. and subsequently processed in the manner of Example A to produce starting material, hereinafter known as product D, and having the same formula as that of Example A except that C1'IH31 is substituted for CuHzs therein.

EXAMPLE E 116 parts of caproic acid and 104 parts of reactant A are condensed in the manner as described in the previous examples and the resulting reaction mass is subsequently processed in the same manner as that set forth in the processing of that of Example A.

The reaction product has the same formula as that of Example A, except that C5H11 is substituted for C11H23 therein, and is hereinafter known as product E.

EXAMPLE F 284 parts of stearic acid and 104 parts of reactant A are heated in the like manner as described in previous, examples, and the resulting reaction mass is then introduced into an aqueoussolution of 110 parts monochlorpropionic acid and 80 parts of caustic soda. The process is carried out in the same manner as described in the previous examples and there is produced a product having the same formula as that of Example A, except that CnHss is substituted for C11H2a and C2H4-COONa for the CI-Ia--COONa therein, and is hereinafter known as product F.

. EXAMPLE G 290 parts dodecyl benzoic acid and 104- parts of reactant A are condensed in the manner described in Example D and the resultant mass is processed in the manner of Example D, whereby there is produced a novel compound having the same formula 'as that of Example A, except that C12H25C6H4 is substituted for CHI-I23 therein, and is hereinafter known as product G.

EXAMPLE H EXAMPLE I 1 mol of lauric fatty acid and 1 mol of ethylenediamine (NH2C2H4NH2) are added together and then heatedin the presence of an inert solvent such as toluol amounts sufficient to dissolve the same. This solution is maintained at a temperature of approximately 110 C. This heating is carried out under a condenser through wh'ichpass vapors which consist of some of the solvent and water of reaction as well as small amounts of unreacted amine. These products are caught in a collector from which the water of reaction is removed and the condensed toluol and collected amine are returned to the reat 110 C. under the aforesaid conditions until 0.9 mol of water is collected. Then a vacuum of approximate- 1y mm. of mercury is applied to the reacting vessel and the temperature maintained at C. until all of the solvent and an additional 0.1 mol of water have been removed. To the resulting mass is added 1 mol of monochloracetic acid and this mixture is heated to a temperature of approximately C., whereupon the temperature of the mass will spontaneously rise to C. By the application of external heat the mass is maintained at said temperature at approximately 170 C. until a one part sample thereof when dissolved in 100 parts of aqueous solution of sodium hydroxide having a pH of approximately 9 provides a clear solution. 1 mol of this mass so produced is added to an aqueous solution containing 1 mol of sodium hydroxide. The entire mass is heated to approximately 80 C. whereupon there is formed the sodium salt of said mass, having the following formula:

The aforesaid salt, whose structural formula is shown in this example may be produced in still another way. Instead of adding the monochloracetic acid at the stage previously shown, there first may be prepared an aqueous solution containing 2 mols of sodium hydroxide and one mol of monochloracetic acid. The temperature of this solution is reduced below 15 C. and preferably 5 to 10 C. and while maintained at said reduced temperature and being constantly agitated there is added thereto one mol of the lauric acid-ethylene diamine reaction mass. While being constantly agitated, the temperature of the mass is raised over a one hour period to about 95 C. Then the temperature of this constantly agitated mass is maintained at 95 C. for an additional 3 hours or until a sample thereof in 100 parts of water will be clear and the pH is no longer subject to change on further heating of the mass at that temperature.

1 mol of the last defined compound is added to a solution containing one mol of caustic soda and one mol of chlorhydrin dissolved in water at a temperature not exceeding 15 C. and preferably between 5 to 10 C. After the addition at said low temperature, the mass is continuously agitated and while in the state of agitation its temperature is raised over about a one hour period to 95 C. and is further continuously agitated and maintained at said temperature for an additional 3 hours, all of this being done under a reflux condenser. During said 3 hour period, the pH of the mass continuously decreases.

At the expiration of that 4 hour period the pH of 1 part,

of the mass when dissolved in 100 parts of water will be 8.5. The 1 part sample when dissolved in 100 parts of water and having a pH of 8.5 in the water, provides a clear solution and is the same product as that of Example A.

EXAMPLE K By following the same procedure as that set forth in Example I with the only difference being that one mol of glycerine chlorhydrin (CH2CICHOH-CH2OH) is substituted for the mol of ethylene chlorhydrin there is produced another one of my starting materials, hereinafter known as product K, and having a formula the same as that of Example A, except that CHzCHOHCI-IzOH is substituted for C2H4OH of Example A.

EXAMPLE L By following the same procedure as that set forth in Example I with the only difference being that one mol of pentaerythritol chlorhydrin (CH2CLC(CH2OH)3) is substituted for the mol of ethylene chlorhydrin there is produced another one of my starting materials, hereinsmroduct L, andahav-inga formula-the same. asithat of Example. A, except that H Q QH. is substituted for -,C2H4 OH of Example. EXAMPLE M B y. following, the same procedure as thatv set forth 1 ExanipleJ with :the .only difference being that one mol .ofi n y y my st n qrhy ri (ClCHz-COCl-Iz-OH) s smr oy d instead of eme m l of s y sne hlqrhy rin theretis produced another one ofmy starting materials hereinafter known as product M, and haying'a.. formula i i $1 m383N1 1? A 1 h CHzCOCHzOH;

s-subjst t dfi HtQHd Ex mp e A. he enne employed in this example may be prepared by employing the well-known method consisting essentially of the dis tillationof 2 mols of hydroxy aceticacid with one .mol of calcium carbonate, after which the ketonenis chlorinated to, provide the. above reactant.

CHzCOCHOHOI-I is substituted for C2H4QH of Example A. The partieular ketone;reactantemployed in this example maybe produced: by the distillation of one mol of dihydroxyacetic acid, one. mol of hydroxy acetic acid and onemol of calcium carbonate after which the distillation product is. chlorinated.

v EXAMPLE P By following the same procedure as that set forth in Example .1 with the only differencesbeing that one mol of monoch-lorlactic acid CH= 1. H H QH is employed-iinsteadof the one mol o-fmonoch'loracetic acid sq that there is produced still another of mystarting material, hereinafter known as product P, having the same formnlaasthat of ExampleA, except that CHzCHOHCOONa is substituted for CHzCOONa of Example A. In this production I prefer to use the aqueous method as set forthinExampleL EXAMPLE- Q Employingthe same, procedure as that set forth in W "le'iA xcept that l mol of capric acid and-1 mol I i nttB andl mol of monochlorpropionic acid are substitixtedforth lauric acid, reactantA and monochlor'actic acid, so that there is produceda startingmaterial, hereinafter known as product Q, having the following formula:

Employingthesamep-rocedure as that set forth in.

rawl A'tex e ti hatt .191 tarts-1 sislt. 391- q z ast pt C andlmol -m nq hlqrla t c a d ar =9 vlQ ssii r eae a ti qid reac ant 1A an lora tie ac h re s; p vided a star ing 1 formula:

3 m s enmt-rcoeN fona-n. n onn, emotion-doom. EXAMPLE S Employingthe same procedure. as, that. set forth. in

ExampleA, except that 1 mol of myristicacid, lrmoleofreactant D- and 2- mols.- of potassiumhydroxide are-used; in place of the lauric acid, reactant A andcausticisoda are used to provide starting material, hereinafter known s Pr duct 9. armats l w n i emu a n ontoHoHQmo-rr C1:Hl1 -Oo-N-CH;0HoHoH,N-

EXAMPLE T Employing thersan eprocedure. as that set forthist;

Example A, except that l mol of cap ric acid, 1 mol of reactant E, and 1 mol of monochlorethoxyacetic acid re used.inplacei f-the ur c ci eactan A r dimonplllerasst e. siddq: Pro de tar in ma ri ls here na ter n wn sr o ust I havin he ollowi g r ula;

:31 02340 CaHs-OH- 00359 0 Q -Nfoim-o-o nl-N QE QW F P 9.???

EXAMPLE U nnl i s he -P o ur as ha t a m n ExampleT, except that 1 mol'of oleic acid, 1 mol of reactant F and 1 molof monochloracetoacetic acid in place of the lauric acid, reactant A and monochloracetic acid to provide..starting material; hereinafter referred :to asproductU, havingthe, following formula:

C4119 CHQCOCHa-OH CIIHSTQOTNTQH1OHQHCH$ .N

CHIC. 0 CHHTQQQN s EXAMPLE V Employing the same procedure as that set forth in Example A, except that in place of the lauric acid, reactant-A and caus'tic soda, substitute 1-mol of'dodecylbenzenemonocarboxylic acid (C12H25C H4COOH); 1 molof reactant Gand 2 mols of potassium hydroxide, toprovide starting material, hereinafter known as'product V, having the "following formula:

oran -Q 1 0. O. .N AGH g C O CH -N CHa-COOK cam-on The specific monocarboxylic acids, as well as; the;

specific monohalomonocarboxylic acids employed in certain examples, may be replaced by others as may be the various other reactantsin thespecific examples to provide a great number of other starting materials, which diifer from thosejset forth in the examples heretqf r Prior to this inven'tion, it was known thatcationic vtfass qt Y en s. nd. q ic ur c st v a n s sn q sthsr Q. q.4 Q QF e u t n, he.P qdl. s-..-

tion or formation of waterinsglnble compounds a d hi dqi sn" i i' i I ut o aw i 9 l.. ct v as ntr s t t. at 1? hi sal. amputat n. a dt nts' d at. noreaction would occur between them. i

su fase at v agent w. n, uequsl Said amino acid metal salts normally behave anionically in aqueous solutions having a pH above 7, and consequently it was expected that said amino acid metal salts when in aqueous solution together with anionic surface agents that they would be combined physically only and that no chemical reaction would occur therebetween. In the course of my experimentations, 'I have discovered that said amino acid metal salts" could be reacted with certain anionic surface active agents at a pH above 7 to produce water-soluble reaction products. Not only did I make said discovery, but I further discovered that water solutions of such reaction products had viscosities greater than corresponding aqueous solutions of the amino acid metal salts and also exhibited better foaming characteristics than did said amino acid metal salts in very low dilutions under extreme water hardness conditions. Said reaction products are non-toxic and non-irritating to the human skin. They have been found eminently useful as general utility detergents, such as for car washing, dish washing, clothes washing, etc. Said amino acid metal salts when used as components of shampoos sometimes caused slight irritation or stinging of the eyes when such shampoos were used and water solutions thereof acc-identally reached the eyes. I have further discovered that the reaction products of this invention caused practically no irritation or stinging of the eyes when so employed.-

wherein R3 is a hydrocarbon radical, generally aliphatic or aliphatic-aromatic, and having at least 6 carbon atoms and for most purposes 6-20 carbon atoms; Z is either oxygen or sulphur; and x is an integer and being at least 1 and generally 1-5, and preferably 3; M, R, R1 and R2 have heretofore been defined in Formula I.

According to this invention, I react a compound of Formula I with a compound of Formula II to provide thenovel and highly useful compounds of Formula III.

In general this reaction is carried out in a solution containing compounds I and II and to which a quantity of an acidic agent such as a strong mineral acid, as for example hydrochloric, sulphuric or its equivalent, has been added to lower the pH of the solution to a value of approximately 7 to approximately 9 and while maintaining the mass at a temperature between approximately 100-200 F. In this reaction under the aforesaid conditions, the compounds of Formula III are produced, said compounds having high water solubility in spite of the fact that the number of carbon atoms in R3 is 6 or more.

Such compounds of Formula III have an unexpected extremely high water-solubility, while the corresponding salts of cationic compounds are water-insoluble. The resultant aqueous solution can be used directly as a surface active agent, wetting agent or detergent for the purposes i0 indicated for the amino acid metal salts." While the quantities of the compound of Formula I and compound of Formula II may be equimolecular for good yield ofcompounds of Formula III, I may employ an excess of either, and in general the mole ratio of a compound of Formula I to compound of Formula II may be 2 moles of the former to 1-3 moles of the latter.

One of the specific methods which I prefer to employ in carrying out an aspect of this invention is to first dissolve a compound of Formula I in water and then the pH thereof is adjusted to approximately 12-13 (measured electrically) by the addition of aqueous caustic soda if required so that when a compound of Formula II is added thereto, the pH of the solution of I and II will be at least 10 and generally -11. The temperature of said solution is raised to 100-200 F. and preferably in factory practice to approximately F. Then a quantity of a compound of Formula II is dissolved in water in a separate container and this solution is added to said first solution and the mass is maintained in said temperature range while being constantly stirred, and an acidic agent is added thereto to reduce the pH thereof to a value below 10 and in the range of approximately 7 to 9, and preferably of approximately. 8.2 to approximately 8.7. At the end of the acidic agent addition, the stirring is continued and the temperature of the mass maintained for about 10-20 minutes after which the solution is allowed to cool and is a finished product.

The following are specific examples merely given by Way of illustrating the invention and are not to be taken by way of limitation, all parts being given by weight unless otherwise specified.

EXAMPLE 1 An aqueous solution of 400 parts of product A in 600 parts of water is heated to approximately 140 F. and its pH (measured electrically) is adjusted by the addition of aqueous caustic soda to 12-13. While being constantly stirred and maintained at that temperature, there is added a solution of 400 parts of sodium salt of lauryldiethoxyether sulfate:

in 600 parts of water. Then while stirring and the temperature is maintained there is added thereto between about 30-40 parts of hydrochloric acid soltuion (32%) whereby the pH of the mass is lowered to a value in the range of 8.2 to 8.7. Stirring is continued and the temperature maintained for about 10 minutes more. The resultant product is a solution of the novel reaction product having the following formula:

EXAMPLE 2 Employ the same procedure and components as set forth in Example 1 except that only about 200 parts of the sodium salt of lauryldiethoxyether sulfate are used. In this instance, the resultant product is a solution of the novel reaction product whose structural formula is shown in Example 1 together with unreacted product A used, in the approximate proportion of two parts of the former to one of the latter.

Employ the same procedure as that set forth in Example 1, but employthe components indicated in the following Examples 3-23; the quantity of hydrochloric acid solution (32%.) is variable to lower the pH to values indi of said Examples 3-23.

'1.1 12 2%Mli-LE. 3V i'mumna F uovELT summon rnonuc'r 4QQ--parts of product A in 600' parts of; water. 25 0 CHQHOEOHPDH parts of octylmohoethoxyether sulphate sodium salt: 7 CREW-O0N-OHQOHOHOH,N;\

C H1v-e-O+.Vl(CzH O)--SO3 u-Na 5 11 om-coox in 400 parts of water.

F RM A. E BE ZHQN P D C cam-0 EXAMPLE 9. C llH33PCON-C3H4N 7 450- parts of product T in 500 parts of water. 400

H \0HPC0ON8 parts of decyltriethoxy thioether sulfate sodium salt: OsH;1-o,(o:H o.)-.so= cmHz.1-s(c2Hlo)3 sol-Na v in- 600 parts of'water. EXAMBLET 4 15 FORMULA OF NOVEL umc'noumonuc'n 40 O parts of product A in 600 parts of water. 500 @311, canon v: parts t mdecyl tetraethoxvether sulfate SOdlUlIl salt: Camry G 1 came V QLaITIg'z1()-.(CzH4O 4- -SOs-Na CHO Caro ooNa I ll]. Of water. s O. ,F

EQBMULA 01r- NOVEL REACTION Paopucm 7 CMPOH EXAMPLE 1o I 550 parts of product U in 850 parts of water. 500 H sparts of amylphenylpentaethoxy ether sulfate sodium O1.-,Ha -Q.(C:HrQ)4SOa alt CsH11-CsH4O-(C2H4Q)5-SQ3:- Na

EXAMPLE 5 in 750 parts of water. 400 parts of product A in 600 parts of water- 00 OR ULA OF NOVEL, REACTION PRODU T parts of nonylphenoltriethoxy other sulfate sodium salt: 04H, QEQQCHFQE CsH19C6H4O-(C2H40)3-SO3-Na H r-CO I'Q-CHNHQHCH in 750 parts of water. H OEOOOHr-OOONa FORMULA OF NOVEL REACTION PRODUCT CnHu .aH4O-(C2H40)r- .0:

ID /C:H'40H- cumhcofu-cim x EXAMPLE 11 WC QN 40 550 parts of product V in 800 parts of water. 500 G H .C H O (c H Q) -SO parts of tridecyltetraethoxy thioether sulfate potassium salt. EXAMPLE 6 C13H27--S(C2H40)4SO3Na 400 parts of" product Q in. 400 parts of' water, 250 in 750 Parts of water" parts of hexylmonoethoxyether sulfate sodiumsalt: FORMULA OF NOVEL REACTION PRODUCT 6H -Q.-(C HQ)-S0 .N HPOH uoruuum opuovur; REACTION PRODUCT H a- O K CH5. CH: CHgCH-OH iF -(CIHAOh-rSO: CHuoo-N-o112cE-N CH3 H/ CzH4-C00Na EXAMPLES 12-16 5' i. CQH13O--(C:H4Q)-7SOL Employmg thesame procedure as that set forthin- Example 1, except that products. B, K, L, M, and Niare= EXAMPLE 7 respectively substituted for product A to provide novel 5,,

550 parts of product R in 850 parts of'water. 600 reaction products. which differ from the novel reaction parts of stearoylpentethoxy thioether sulfate sodium salt: product whose formula is shown in Example 1, by. sub- 7 stituting for the CzHa-OI-Iradical' thereof, the follow CHI-I35 E (CH-hon EO3 Na ing respective'radicals: CzH4OC2H4-OH,

WHWQHPOE CHzCOCHr-QH, CHzCQCHQH.-QH QUHETC. O.N, C (UH); Q Hn rN ommpflrwoml EXAMPLES 17-20 (111335 8(O2H4;0')5s)a V Employing the same procedure as that set forth in EXAMPLE 8 Example 1, except that products D,' E', G-and- H are respectively substitutedfor-product-A toprovide novel 4 5O; pa1;ts o produot S1 50) parts o f'watert 350 reaction products, which'ditfer'from; the-- novel reactionp artsofioctylpheuohdiethogty thioether sulfate potassium; product whoseformula is shownin Example 1, by salt: substitutingfortheCiiHza radicalthereof thefollowing C H 1';---CsI I 1S--t-(C2H4O)a=--SO:;K, respective radicals:

in 400 parts of water. CrzH31, Cal-I77, CmPIzs-CsI-IsBQdQmI-Ia.

13 EXAMPLE 21 EXAMPLES 22 AND 23 Employing the same procedure as that set forth in Example 1, except that products C and F respectively are substituted for product A to provide novel reaction products which differ from the novel reaction product whose formula is shown in Example 1, by substituting CzH4-COONa for the CH2COONa and also substituting C9H19 and CnHss respectively for C11H23.

EXAMPLES 24-36 Employing the same procedure as that set forth in Example 3, except that, instead of product A, there are respectfully substituted compounds which are the same as product A, except that the H of the NH attached directly to the CO group thereof is replaced by the following respective radicals: CH3, -C2Hs, -C3H'z,

whereby there are produced a number'of other novel reaction products whose formulas are the same as the formula of the novel reaction product whose formula is within the definition of Formula III and shown in Example 3, except that the aforesaid respective radicals replace the H of the NH connected directly to the CO thereof.

Following the same procedure as that set forth in Ex ample 1 and employing 1 mol of any of said other starting materials, such as products B-H, J-N, P-V, respectively, and 1 mol of any of the other specific compounds of Formula II employed in Examples 1-36, a great number of other novel reaction products whose formulas are that of Formula III may be produced; and in addition, the specific reactants employed may differ from those employed herein, .in varying R, R1, R2, and R3 within the definitions thereof, to provide a great number of other compounds of Formula III.

It is to be understood that instead of first adjusting the pH of the compound of Formula I to 12-13 before the addition of the compound of Formula 11, any other method may be employed to obtain the condition whereby the pH of the solution of I and II is at least and preferably 10.5-11 before the addition of the acidic agent to lower the pH of the mass to approximately 7 to approximately 9. For example, I and II may be dissolved together and this solution may, by the addition of caustic soda when required, have its pH adjusted to at least 10, and then at IOU-200 F. is ready for the addition of the acidic agent to lower its pH to approximately 7 to approximately 9. If desired, the required amount of acidic agent may be added either before or after the solution of pH of at least 10 is brought to a temperature in the range of 100-200" F.

Since certain changes in carrying out the aforesaid processes and certain modifications in the compositions which embody the invention may be made without departing from its scope, it is intended that all matter contained in the description shall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended to cover all the generic and specific features of the invention herein described, and all statements of the scope of the invention which as a matter of language might be said to fall therebetween.

I claim: l. A compound of the following formulai R1 Rr-OH R-C 0I iR:-

H Rr-GOOM in which R is a hydrocarbon radical of 4 to 18 carbon atoms; R2 is an organic group selected from the class consisting of (a) aliphatic hydrocarbon groups of 1-4 carbon atoms; (b) hydroxy substituted aliphatic hydrocarbon groups of 1-4 carbon atoms, (0) aliphatic ether groups, each of said ether groups having an ether oxygen linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (d) aliphatic ether groups, each of said groups having an ether oxygen linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms, (e) aliphatic keto groups, each of said groups having a carbonyl linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (f) aliphatic keto groups, with each of said groups having a carbonyl linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms; R1 is selected from the group consisting of hydrogen and monovalent radicals otherwise defined in said (a)-(f); R3 is a hydrocarbon radical of 6 to 20 carbon atoms; Z is an atom selected from the group consisting of oxygen and sulfur; x is a number of at least 1 and no greater than 5; and M is an alkali metal.

2. A compound of the following formula:

CHr-CO ON:

in which R is a hydrocarbon radical of 4 to 18 carbon atoms, R3 is a hydrocarbon radical of at least 6 to 20 carbon atoms and x is 1-5.

3. A compound of the following formula:

CHr-OO ON:

Rs-O-(CzHrO) r:

in which R3 is a hydrocarbon radical of at least 6 to 20 carbon atoms and x is 1-5.

5. A compound of the following formula:

CHz-CO 0N8 in which R3 is a hydrocarbon radical of at least 6 to 20 carbon atoms, and x is 1-5.

6. A compound of the following formula:

CHr-COONa References Cited in the file of this patent UNITED STATES PATENTS 2,103,872 Schoeller Dec. 28, 1937 2,329,406 Mauersberger Sept. 14, 1943 2,391,830 Jayne et a1 Dec. 25, 15*45 OTHER REFERENCES Sisley et 211.: Encyclopedia of Surface Active Agents, 10 1952, page 502. 

1. A COMPOUND OF THE FOLLOWING FORMULA: 